CN103668089A - Preparation method for sputtering titanium dioxide nanorod arrays on flexible substrate - Google Patents
Preparation method for sputtering titanium dioxide nanorod arrays on flexible substrate Download PDFInfo
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- CN103668089A CN103668089A CN201310639266.6A CN201310639266A CN103668089A CN 103668089 A CN103668089 A CN 103668089A CN 201310639266 A CN201310639266 A CN 201310639266A CN 103668089 A CN103668089 A CN 103668089A
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Abstract
The invention discloses a preparation method for sputtering titanium dioxide nanorod arrays on a flexible substrate. The preparation method comprises the steps: flexible substrate cleaning: carrying out ultrasonic cleaning successively with acetone, ethanol and deionized water; substrate sputtering: adopting direct-current sputtering of a titanium target, wherein sputtering gas is pure argon gas and pure oxygen gas; and subsequent sputtering: continuing direct-current sputtering with the sputtering gas unchanged. The method is simple in operation, enables the thickness of the obtained nanorod arrays to be controlled by the magnetron sputtering time and the magnetron sputtering temperature, has stable product properties and uniform film forming, can be used for large-scale preparation, and is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of preparation of monodimension nanometer material titanium dioxide, specifically, that relate to is the preparation method of sputter titanic oxide nanorod array in a kind of flexible substrates.
Background technology
Nano material, because having the characteristic properties such as small-size effect, surface effects, quantum size effect, macro quanta tunnel effect, Dielectric confinement effect, shows the not available various high-performances of conventional material.In nano materials research field, nano titanium oxide, as a kind of functional semiconductor material, has purposes very widely in fields such as environment protection, opto-electronic conversion, coating industry and Industrial Catalysis.Nanometer titanic oxide material have inexpensive nontoxic, particle diameter is little, particle aggregation is few, pattern stable homogeneous, can recycling etc. advantage and enjoying favor aspect sewage disposal, purifying air.
The anatase titanium dioxide nanometer stick array of flexible substrate load has broad application prospects at aspects such as the storage of sun power and utilization, opto-electronic conversion, especially the application aspect double-faced flexible dye sensitization solar battery, to save the required high-temperature calcination stage of Crystalline Phase Transition of Titania, greatly improve the activity of light anode.By magnetron sputtering method, prepare anatase titanium dioxide nanometer stick array light anode, adopt light splitting technology to make sunlight by light anode and transparent in electrode incident simultaneously, can effectively improve the firing rate of light-sensitive coloring agent.
The method of preparing at present titanium dioxide nano-rod mainly contains hydrothermal synthesis method, spin-coating method and anonizing, and the report of preparing titanic oxide nanorod array about direct employing magnetron sputtering method is few.As the patent of invention that China Patent Publication No. is CN102086045A, this patent comprises the steps: 1) tetrabutyl titanate, diethanolamine and ethanol are mixed after, add dropping liquid, stirring and evenly mixing, after ageing, obtains whirl coating liquid; Described dropping liquid is comprised of water, ethanol and concentrated hydrochloric acid; 2) by described step 1) the whirl coating liquid that obtains is coated in substrate, after dry and thermal treatment, at described substrate surface, obtains rutile TiO
2film; 3) by described step 2) gained rutile TiO
2film mixes with presoma I, reacts in 190 ℃, reacts the complete TiO of obtaining
2one-level nanometer stick array; Described presoma I is TiCl
3naCl saturated aqueous solution, the pH value of described presoma I is 0.25; 4) by described step 3) gained TiO
2one-level nanometer stick array mixes with presoma II, reacts in 190 ℃, reacts the complete described TiO that obtains
2secondary nanorod array; Described presoma II is TiCl
3naCl saturated aqueous solution, the pH value of described presoma II is 0.25-1.20.This patent is to utilize the method applying first to obtain one deck titanium film, then adopt Hydrothermal Growth nanometer stick array, process more complicated, in the present invention, be to utilize the direct sputter nanometer stick array of magnetically controlled sputter method, have that equipment is simple, low price, film forming evenly, can be used for the advantages such as masking in enormous quantities.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides the preparation method of sputter titanic oxide nanorod array in a kind of flexible substrates.
In flexible substrates, a preparation method for sputter titanic oxide nanorod array, is characterized in that, comprises the steps:
(1) flexible substrates is cleaned: use successively acetone, alcohol, deionized water ultrasonic cleaning;
(2) substrate sputter: adopt d.c. sputtering titanium target, sputter gas is pure argon and purity oxygen;
(3) follow-up sputter: proceed d.c. sputtering, sputter gas is constant.
The ultrasonic time of the described acetone of step (1), alcohol and deionized water is respectively 10 minutes.
Step vacuumizes magnetron sputtering chamber in (2), makes its vacuum tightness be less than 9.0 * 10
-4pa.
Regulating the distance of flexible substrates and target in step (2) is 10～20 centimetres, selects 99.99% pure titanium target as the sputtering target of Ti thin film deposition.
In step (2), the power of substrate sputter is 150-200 watt, and sputtering time is 0.5 hour.
The purity of the described pure argon of step (2) is more than 99.99%, and flow is 20-80sccm, and the purity of purity oxygen is more than 99.99%, and flow is 20-80sccm, and gas pressure intensity is 0.3-0.8Pa.
The power of the described sputter of step (3) is 150-250 watt, and sputtering time is 1-6 hour.
Compared with prior art, the present invention has overcome additive method to be needed during the course obtain solution or the shortcoming such as heats, utilize magnetron sputtering direct sputter layer of titanium dioxide nanometer stick array in flexible substrates, and by increasing base reservoir temperature, make the nanometer stick array after sputter more evenly smooth, and the speed of growth is faster.The present invention is easy and simple to handle, low price, and reaction conditions is gentle, and the thickness of the nanometer stick array that obtains of magnetically controlled sputter method can control by sputtering time and temperature, and film forming is even, can be used for big area and prepares film, is applicable to suitability for industrialized production.The nanometer rod making can have application prospect at aspects such as photoluminescence, photochemical catalysis.
Accompanying drawing explanation
By reading the detailed description of non-limiting example being done with reference to the following drawings, it is more obvious that other features, objects and advantages of the present invention will become:
Fig. 1 is that the SEM picture of the embodiment of the present invention 1: a is front shape appearance figure, and b is cross-section morphology figure;
Fig. 2 is the TEM picture of the embodiment of the present invention 1;
Fig. 3 is that the SEM picture of the embodiment of the present invention 2: a is front shape appearance figure, and b is cross-section morphology figure;
Fig. 4 is that the SEM picture of the embodiment of the present invention 3: a is front shape appearance figure, and b is cross-section morphology figure;
embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art further to understand the present invention, but not limit in any form the present invention.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make some distortion and improvement.These all belong to protection scope of the present invention.
Embodiment 1:
(1) flexible substrates of 2 * 2 centimetres is cleaned 10 minutes in acetone, alcohol and deionized water for ultrasonic successively;
(2) the flexible substrates sheet in (1) is placed in magnetron sputtering chamber, adopts d.c. sputtering titanium target, first sputter one deck substrate titanium dioxide, 185 watts of sputtering powers, sputtering time 0.5 hour, pure argon flow 40sccm, oxygen flow is 20sccm, back end vacuum tightness 8.0 * 10
-4pa, sputtering pressure 0.6pa;
(3) flexible substrates in (2) is proceeded to sputter, 185 watts of sputtering powers, sputtering time 1 hour, gas flow is constant.
As shown in Figure 1, be the TiO of magnetron sputtering gained
2nanometer stick array, can see that positive nanoparticle size is smaller, and the pattern of nanometer stick array is also not obvious, and its thickness only has 90 nanometer left and right.The viewed result of TEM is consistent with the result of SEM, the length of nanometer stick array between 70-100 nanometer, arrayed high-sequential (as shown in Figure 2).
Embodiment 2:
(1) flexible substrates of 2 * 2 centimetres is cleaned 10 minutes in acetone, alcohol and deionized water for ultrasonic successively;
(2) the flexible substrates sheet in (1) is placed in magnetron sputtering chamber, adopts d.c. sputtering titanium target, first sputter one deck substrate titanium dioxide, 185 watts of sputtering powers, sputtering time 0.5 hour, pure argon flow 40sccm, oxygen flow is 20sccm, back end vacuum tightness 9.0 * 10
-4pa, sputtering pressure 0.6pa;
(3) flexible substrates in (2) is proceeded to sputter, 250 watts of sputtering powers, sputtering time 3 hours, gas flow is constant.
As shown in Figure 3, the titanic oxide nanorod array of gained is the good anatase crystal of crystallinity, positive nanoparticle size obviously increases compared with Fig. 1 a, and the thickness of its nanometer stick array is also increased to 288 nanometers left and right, and the thickness of whole sputtered film reaches 468 nanometers.
Embodiment 3:
(1) flexible substrates of 2 * 2 centimetres is cleaned 10 minutes in acetone, alcohol and deionized water for ultrasonic successively;
(2) the flexible substrates sheet in (1) is placed in magnetron sputtering chamber, adopts d.c. sputtering titanium target, first sputter one deck substrate titanium dioxide, 185 watts of sputtering powers, sputtering time 0.5 hour, pure argon flow 40sccm, oxygen flow is 20sccm, back end vacuum tightness 8.0 * 10
-4pa, sputtering pressure 0.6pa;
(3) flexible substrates in (2) is proceeded to sputter, 215 watts of sputtering powers, sputtering time 6 hours, gas flow is constant.
Fig. 4 is the SEM picture of titanic oxide nanorod array, discovery is after long sputter in 6 hours, its nanometer stick array is still keeping high-sequential, its thickness obviously increases, be about 775 nanometer left and right, the thickness of whole sputtered film also reaches 1 micron of left and right, and positive nanoparticle size also significantly increases and occurs agglomeration.
Above specific embodiments of the invention are described.It will be appreciated that, the present invention is not limited to above-mentioned specific implementations, and those skilled in the art can make various distortion or modification within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (7)
1. a preparation method for sputter titanic oxide nanorod array in flexible substrates, is characterized in that, comprises the steps:
(1) flexible substrates is cleaned: use successively acetone, alcohol, deionized water ultrasonic cleaning;
(2) substrate sputter: adopt d.c. sputtering titanium target, sputter gas is pure argon and purity oxygen;
(3) follow-up sputter: proceed d.c. sputtering, sputter gas is constant.
2. the preparation method of sputter titanic oxide nanorod array in flexible substrates according to claim 1, is characterized in that, the ultrasonic time of the described acetone of step (1), alcohol and deionized water is respectively 10 minutes.
3. the preparation method of sputter titanic oxide nanorod array in flexible substrates according to claim 1, is characterized in that, step vacuumizes magnetron sputtering chamber in (2), makes its vacuum tightness be less than 9.0 * 10
-4pa.
4. the preparation method of sputter titanic oxide nanorod array in flexible substrates according to claim 1, it is characterized in that, regulating the distance of flexible substrates and target in step (2) is 10～20 centimetres, selects 99.99% pure titanium target as the sputtering target of Ti thin film deposition.
5. the preparation method of sputter titanic oxide nanorod array in flexible substrates according to claim 1, is characterized in that, in step (2), the power of substrate sputter is 150-200 watt, and sputtering time is 0.5 hour.
6. the preparation method of sputter titanic oxide nanorod array in flexible substrates according to claim 1, it is characterized in that, the purity of the described pure argon of step (2) is more than 99.99%, flow is 20-80sccm, the purity of purity oxygen is more than 99.99%, flow is 20-80sccm, and gas pressure intensity is 0.3-0.8Pa.
7. the preparation method of sputter titanic oxide nanorod array in flexible substrates according to claim 1, is characterized in that, the power of the described sputter of step (3) is 150-250 watt, and sputtering time is 1-6 hour.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106987814A (en) * | 2017-04-17 | 2017-07-28 | 烟台睿创微纳技术股份有限公司 | A kind of preparation method of the titanium oxide thermosensitive film of micro-metering bolometer |
| CN107699855A (en) * | 2016-08-08 | 2018-02-16 | 中国科学院福建物质结构研究所 | A kind of titanium dioxide nano-rod film with high photocatalysis efficiency and preparation method thereof |
| CN107774289A (en) * | 2016-08-29 | 2018-03-09 | 中国科学院福建物质结构研究所 | A kind of photocatalytic cleavage water hydrogen manufacturing film catalyst and its preparation method and application |
| CN109132999A (en) * | 2018-09-05 | 2019-01-04 | 天津瑞晟晖能科技有限公司 | Metal oxide nano array film and preparation method thereof and the electrode comprising it, battery |
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| CN101944439A (en) * | 2009-07-09 | 2011-01-12 | 中国科学院大连化学物理研究所 | Preparation method for TiO2 nanometer rod array of dye sensitized solar cell |
| CN101950605A (en) * | 2010-07-23 | 2011-01-19 | 四川大学 | Technology for obtaining porous high-purity anatase phase titanium dioxide film on surface of flexible matrix material |
| CN102157264A (en) * | 2011-01-26 | 2011-08-17 | 浙江大学 | Preparation method of composite membrane for dye sensitized solar cells |
| JP2013016369A (en) * | 2011-07-05 | 2013-01-24 | Kyushu Institute Of Technology | Manufacturing method of anode for dye-sensitized solar cell and manufacturing method of dye-sensitized solar cell |
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Patent Citations (5)
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| CN101944439A (en) * | 2009-07-09 | 2011-01-12 | 中国科学院大连化学物理研究所 | Preparation method for TiO2 nanometer rod array of dye sensitized solar cell |
| CN101838794A (en) * | 2010-05-31 | 2010-09-22 | 苏州羿日新能源有限公司 | Method for preparing titania film by using gas flow reaction sputtering under middle gas pressure and method for preparing solar cell |
| CN101950605A (en) * | 2010-07-23 | 2011-01-19 | 四川大学 | Technology for obtaining porous high-purity anatase phase titanium dioxide film on surface of flexible matrix material |
| CN102157264A (en) * | 2011-01-26 | 2011-08-17 | 浙江大学 | Preparation method of composite membrane for dye sensitized solar cells |
| JP2013016369A (en) * | 2011-07-05 | 2013-01-24 | Kyushu Institute Of Technology | Manufacturing method of anode for dye-sensitized solar cell and manufacturing method of dye-sensitized solar cell |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107699855A (en) * | 2016-08-08 | 2018-02-16 | 中国科学院福建物质结构研究所 | A kind of titanium dioxide nano-rod film with high photocatalysis efficiency and preparation method thereof |
| CN107774289A (en) * | 2016-08-29 | 2018-03-09 | 中国科学院福建物质结构研究所 | A kind of photocatalytic cleavage water hydrogen manufacturing film catalyst and its preparation method and application |
| CN106987814A (en) * | 2017-04-17 | 2017-07-28 | 烟台睿创微纳技术股份有限公司 | A kind of preparation method of the titanium oxide thermosensitive film of micro-metering bolometer |
| CN109132999A (en) * | 2018-09-05 | 2019-01-04 | 天津瑞晟晖能科技有限公司 | Metal oxide nano array film and preparation method thereof and the electrode comprising it, battery |
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